二维共价有机框架薄膜的表面合成及光催化性质研究

Two-dimensional covalent organic framework possesses the merit of designable and tunable structure, highly ordered pore structure, high specific surface area, high crystallinity, and has shown an important potential research value in the photocatalytic hydrogen evolution. In order to develop a highly efficient photocatalytic system based on two-dimensional covalent organic framework for hydrogen evolution and to solve the problems related to the preparation of high-quality two-dimensional covalent organic framework, this project is to prepare two-dimensional covalent organic framework films with high crystallinity and controllable orientation on the substrate surface by designing suitable monomer molecular structures, regulating the interfacial properties of substrates and optimizing the growing kinetics conditions; to develop the two-dimensional covalent organic framework film based photocatalytic system with excellent performance of hydrogen evolution through co-catalyst modification and interfacial property optimization. Coupling with the theoretical calculation, the relationship between the molecular structure, interfacial properties of two-dimensional covalent organic framework film based photocatalytic system and its photocatalytically hydrogen producing activity will be explored and revealed in depth. Based on the research on the key issues such as the regulation of interfacial growth and the relationship between the structure and photocatalytic performance of two-dimensional covalent organic framework films, the project will propose a new approach for high-quality preparation and photocatalytic performance exploration of two-dimensional covalent organic framework films. These ideas and new methods have important theoretical and practical significance for promoting the exploration of two-dimensional covalent organic framework film’s potential properties and applications.

二维共价有机框架材料具有结构可设计调控、孔结构高度有序、比表面积高、结晶性好等特点，在光催化产氢方面表现出重要的潜在研究价值。为了发展具有高效产氢性能的二维共价有机框架光催化体系、解决二维共价有机框架制备的相关问题，本项目拟基于单体分子结构设计、基底界面性质调控、生长动力学条件优化，在基底表面制备高结晶性、取向生长的二维共价有机框架薄膜材料；通过共催化剂修饰和界面性质优化，发展具有高效光催化产氢性能的二维共价有机框架薄膜催化体系；结合分子结构模拟，深入探究和揭示二维共价有机框架薄膜结构及表界面性质与光催化产氢活性之间的关系。本项目通过对二维共价有机框架薄膜的界面生长调控及结构与性能之间的关系等关键问题的研究，将为二维共价有机框架薄膜材料的高质量制备、光催化性能探索提出新思路和新方法，对于推进二维共价有机框架薄膜材料的性质和应用探索具有重要的理论意义和实践意义。

二维共价有机框架（2D COF）材料具有结构可设计调控、孔结构高度有序、比表面积高、结晶性好等特点，在光催化产氢方面表现出重要的潜在研究和应用价值。本项目从单体分子结构筛选出发，设计、合成了多种高结晶性、高稳定性亚胺类2D COF材料。采用稳态光谱和飞秒激光瞬态光谱，结合含时密度泛函理论计算，分析了2D COF材料的光激发动力学过程，为光活性2D COF材料的筛选提供了基础。通过基底表面修饰、固液界面反应装置设计、反应动力学控制等手段，实现了高结晶性、高取向性2D COF薄膜在导电玻璃、氧化硅等基底表面的生长。结合2D COF薄膜的界面合成调控，以二氧化钛纳米管阵列为基底，建立了可用于高效光电协同催化产氢的2D COF薄膜催化体系。本项目通过对2D COF薄膜的界面生长调控、结构与性能之间的关系等关键问题的研究，为2D COF材料的高质量制备、光电化学性质探索、催化性提升等提出新思路和新方法，对于推进2D COF材料的性质和应用探索具有重要的理论和实践意义。